Dehydrating organic liquids



J1me 1937- T. wA| Is El AL 2,084,419

'DEHYDRATING ORGANIC LIQUIDS Filed March 23, 1932 i 2 Sheets-Sheet 1 In venfors By Aflorngs *Zza.

June 22, 1937.

1'. WALLIS ET AL 2,034,419 DEHYDRATING ORGANIC LIQUIDS Filed March as, 1932 2 Sheets-Sheet 2 .95 .2.

In venfor Patented June 22, 1937 ,v UNITED STATES 2,084,419 I DEHYDRATING ORGANIC LIQUIDS Theodor Wallis, Dessau-Ziebigk in Anhalt, and

Oskar Falek, Wiederitzsch, near Leipzig, G

many, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Ger- 1 Applieatioiin March 23,

1932, Serial No. 600,130.

Germany Match 30, 1931 3 Claims.

Our present invention relates to "a new method for dehydrating organic liquids and apparatus therefor.

One of its objects is to provide a new dehy- 5 drating agent which easily can be regenerated.

Another object of our invention is to provide a process in which the complete or nearly complete dehydration-is carried out in a minimum of time by bringing the liquid to be dehydrated in contact with the dehydrating agent in the gaseous.

state.

An additional object of our invention is the new apparatus for carrying out continuously the dehydration of the liquid and regeneration of the drying agent.

Further objects of our invention will be seen figzm the detailed specification following herea er. It is known that fractional distillation is not applicable for separating from organic liquids water contained in them in those cases in which the boiling points of the constituents are close together, or in which the liquid forms an azeotropic mixture with water, or in which the organic compound undergoes decomposition when heated with water.

As examples there may be named from among the large number of such casesz-acetal, aldehyde-ammonia, formic acid, amylene hydrate,

crotonaldehyde, acetic acid, isobutyl alcohol,

isopropyl alcohol, piperidine and pyridine.

Processes are known for drying organic liquids by the addition of dehydrating agents which bind water (calcium oxide, calcium chloride, so-

5 dium hydroxide, potassium carbonate, sodium sulfate or copper sulfate); in most of the cases above referred to, however, these processes do not lead to the desired result or the dehydration is unduly slow. 40 The subject of the present invention is a proces in which there is used as dehydrating agent a calcium sulfate which is obtained by subjecting commercial plaster of Paris, advantageously in ground condition, to a temperature of about 5 160 to 180 C. or higher, until the water of crystallization has been completely expelled. Calcium sulfate (anhydrous) which has been thus dehydrated removes remarkably quickly 6.6 per cent of its weight of water from organic liq- 50 uids, reverting to the non-hardening semi-hydrate; it does not part with this water even when heated up to 110 C., so that liquids which have been dehydrated by its use can be obtained in an anhydrous state by distillation either at nor-.-

:malprenureorunderreducedpreasure.

'A further advantage in the use of calcium fate which has been dried at about 160 C. or higher lies in its neutral reaction and in the ease with which it can be regenerated at a temperature of about 160 to 180 C.; in the latter respect it is approached by no other drying agent.

Naturally instead of preparing the anhydrous calcium sulfate from the semi-hydrate .(plaster of Paris) it is also impossible to start from the dihydrate (mineral gypsum) and to dehydrate this directly at a temperature of about 160 C. or higher so as to obtain anhydrous calcium sulfate.

- According to the present invention, organic liquids are dehydrated by causing the dehydrating agent (that is to say calcium sulfate which has been completely dehydrated at about 160 to 180 C. or higher) to act on the vapors of the liquid which is to be dehydrated. It was not to be expected that the short time of contact of the vapor with the dehydrating agent would suflice for the complete absorption of the water from the vapor and the production of a condensate which is free from water. By means of suitable apparatus it is possible in accordance with the invention to conduct the dehydrating of the vapors and the regeneration of the dehydrating agent periodically without removal of the latter from the apparatus. "On the other hand, it is also possible in a completely continuous mode of operation to cause the dehydrating agent to circulate first in countercurrent to the vapors, which are thereby freed from the water, and then through a more highly heated portion of the apparatus, where it gives up its waterand from which it returns'to the portion of the apparatus traversed by the vapors.

As has been above indicated, the invention is particularly suited to the dehydration of liquids whose. boiling points are close to that of water and especially in cases in which constant boiling mixtures are formed, for example in the case of acetal, acetaldehyde, acetaldehyde-ammonia, formic acid, amylene hydrate, ethyl alcohol, propyl alcohol, isopropyl alcohol, isobutyl alcohol, chloral, chlorhydrin, chloracetone, pyridine and its homologues, cyclohexanol and others.

The content of water in the liquids to be dehydrated may vary within wide limits, especially in the continuous mode of operation, wherein care must be taken that for each 5 parts of sulwater vapor present in the vapors obtained by distillation of the liquid, to parts of dehydrated calcium sulfate are brought into con tact with the vapors in the same interval of time. I In practicathe limitis dcpendenton thequertion as to whether the expenditure of steam which would be required for fractionating the liquid is substantially more economical than the dehydration of the necessary quantity of calcium sulfate; in the case of substances which can be fractionated only with difllculty such as isopropyl alcohol and isobutyl alcohol this limit is reached at a content of water of about 25-35 per cent. However, the process is also applicable in the case of liquids containing even 80 per cent of water where special circumstances may render its application advantageous. v

The following examples illustrate the process of the invention and an apparatus suitable therefor, reference being made to the accompanying drawings inwhich I v Fig. 1 shows a drying tower, partially in section,

Fig. 2 is a side view (partially in section) of a zo combinatlon of drying tubes for carrying out the dehydration continuously with regeneration I of the dehydrating gypsum,

Fig. 3 shows the combination of Flg."1 seen from above,

Fig. 41s a front view of Fig. 1.

In Figs. 2 toe the same reference are used to indicate the same parts.

Example 1. Periodic mode of operation The apparatus is illustrated in Fig. 1. Through a tower I of height 2 meters anddiameter 10 cm. which contains 150 successive layers 2 each consisting of a fine wire net, a layer of glass rings and 100 grams .of plaster of Paris distributed thereon, there is first passed a current of hot air through the inlet 3 and the outlet 4 or vice versa at about 200 C. until the plaster has been completely dehydrated. There are then passed through the tower through the inlet '3' and the outlet l'ln the course of 2 hours 25 kilos of the vapors of pyridine having a water content of 3 per cent, the pressure being somewhat reduced in order to maintain a boiling temperature of 100 to 110 C.; the contents of the characters tower being held at that temperature by the hot water jacket I. On cooling the vapors leaving the tower at 4 pyridine is obtained in anhydrous state. The alternate dehydration of theicalcium sulfate by means of hot air and of the pyridine 5o vapors by the dehydrated calcium sulfate can be repeated as often as may be desired.

Example 2. Continuous mode of operation The apparatus used is illustratedin Figs. 2 to 4 of the accompanying drawingszlntheseflsurestand laretwodrumsarranged in any desired manner with respect to one another, preferably, however, inclined to 88011 other. tubes and operate in contrary direction so as to cause about 5 tons of calcium sulfate to circulate per hour in the direction shown'by the arrows. Both the drums I and I are provided with Jackets landlinordertoheatthemtothedesiredterm' per-attire. careistakentoensurethatthecah' They are combined" byconveying.

pors of ethyl alcohol of per cent strength at the rate of 4 tons per hour, the vapors being introduced into the drum at l2. Condensation of vapors inside the drum 6 is prevented by suitable external heating with the aid of the jacket 8 so as to maintain a temperature of about 80 to about C. Depending on the duration of the contact between the calcium. sulfate and the vapors, water is withdrawn from the vapors bythe calcium sulfate in a manner which can be completely, controlled, so that there leave the into the upper part of the drum I where it is 4 completely converted into the anhydride. This may be done by acting in counter-current upon the semi-hydrate with heated air or furnace gases having a temperature above 0., so

that it again gives up its water. The hot air enters the drum at H and leaves it at I! after having passed the dust separator l9. Preferably, however, the calcium sulfate is dehydrated inthe drum I by condensing steam of 8 to 10 atmospheres pressure or the vapors of an organic liquid having a boilingpoint of about 160 to C.,. for example orthodichlorobenzene, in a Jacket 9 surrounding the drum, the condensate being returned continuously from the jacket to the vaporizer (not shown); In this case, only a weak circulation of air through the drum 1 is necessitated in order to carry away the steam.

Between the drums and I there may be advantageously interposed a small tower II in which the descending calcium sulfate is freed from any adherent residue of alcohol by a counter-current of superheated steam entering at 2 I; such alcohol is obtained in dilute form by condensation of the vapors leaving the tower at 22. A gas-tight connection between the drums and the tower is advantageously ensured by the conveyer screw ll situated at a lower level than the drums and operating in 'an upwardly in'clined direction, the calcium sulfate being supplied to it through a down pipe 24'. In said pipe 24' always sufilcient calcium sulfate will be present to avoid gas circulation between drums 6 and I. A similar occlusion may be provided at 24. At the other endofthedrumlthegypsum nowintheanhydrous form is conveyed to the drum 0 by the upwardly inclined conveyer screw IO", the gasti'ght connection being likewise reached by providing a down pipe N", where a sufficient amoun of gypsum is allowed toaccumulate.

Example 3. Continuous mode of operation for the dehydration of liquids containing much water The'apparatus describedin Example2ismodifledbyincreaslngthedimensionsofthednunl serving for the dehydration of the calcium sulfate so that its diameterand length are respectiveiytwiceandlyitimesthediameterand lengthofthedrum'inwhichthevaporsofthe liquidaredehydrated.

4.3tonsofisopropyialcoholcf'l0percent strensth-tbatistolaycontainingutomof the same interval of time and in counter-current 26 tons of dehydrated calcium sulfate. Provided that the calcium sulfate is well distributed, a period of contact of 4 to 8 seconds suflices for complete dehydration of the vapors, which leave the drum with a degree of purity of 99.6 to 99.7 per cent. The calcium sulfate is dehydrated in the drum 1 in the mannerv described above.

In order to counteract adherence of the drying agent to the walls of the apparatus, there may be mixed with the calcium sulfate a finely powdered or finely porous inert substance, which diminishes both the friction between the calcium sulfate and the walls of the apparatus and the internal friction of the mass of calcium sulfate and thus practically excludes adherence to the walls of the vessel and caking into lumps. Examples of such substances are silica gel, kieselguhr, talc, fullers earth, clay, iron oxide, sand or coke. In most cases an addition of 2 to 5 per cent of one of these substances sufiices. If necessary the proportion can be increased.

Our new process likewise is of high value when dehydrating mixtures of organic liquids. As well 'known, a great number of organic liquids cannot be separated from a mixture by fractional distillation, if water is present, since a plurality of azeotropic mixtures is formed the boiling points of which are close together. This is the case, for instance, with the mixture of alcohols and other organic compounds obtained in the manufacture of synthetic alcohols and containing, for instance, methyl alcohol, propyl alcohol and other higher alcohols in the presence of water. If, however, such a mixture is dehydrated in the manner described above, the individual constituents can be easily obtained by guiding .the dehydrated vapors leaving the drum 6 .at l3 through one of the known fractionating devices. In this manner, the fractionation of the mixture can be immediately joined with the dehydration.

It is obvious-that our invention is not limited to the examples given above or to the specific details given therein. Thus, for instance, the heating jackets 8 and 9 surrounding drums 6 and I may be devided in several zones, if a difierent heating of different parts of these drums seems necessary. In order to avoid loss of the liquid to be dehydrated, a heating of the ends of drum 6 (not surrounded by the jacket as illustrated in the drawings) may be provided, so that the organic liquid, eventually absorbed by the gypsum, is expelled. Then the provision of tower 2| may be dispensed with.

On the other hand it may be necessary to cool the calcium sulfate dehydrated at 180 C. or at a somewhat higher temperature before entering the drum 6. A'cooling of the dehydrating agent likewise can be necessitated in the drum 6, since the formation of the semihydrate is an exothermic reaction, so that in the case of high water absorption the reaction temperature becomes too high. Under these conditions advantageously a heating jacket at 24 is provided as mentioned above.

when dehydrating organic liquids having a somewhat higher boiling point, the application of reduced pressure may be foreseen.

The dehydration of the calcium sulfate semihydrate (or eventually dihydrate) is carried out, as mentioned above, at 160 to-180 C.; it may be performed quicker if desired at a higher temperature, care being taken, however,- that'no overburning of the gypsum takes'place. Since the temperature of the dehydrating agent during water absorption shall not be considerably higher than the boiling point of theliquid-to be dehydrated generally 160 to 180 C. are suflicient for the regeneration of the anhydrous sulfate.

These and various modifications and changes in details of construction and arrangement of parts are considered to be within the spirit of the invention and the scope of the following claims.

What we claim is:--

1. A process for dehydrating continuously organic liquids which at the beginning of the process contain some water and do not chemically react with calcium sulfate, which comprises completely dehydrating calcium sulfate at about 160 a to about 180 C., vaporizing the liquid to be dried, distributing the anhydrous calcium sulfate, passing the vapors of the liquid through the calcium sulfate in countercurrent and in such an amount that by absorption of water the anhydrous calcium sulfate is converted into the semihydrate, withdrawing the latter from the dehydration zone, subjecting it to a temperature of about 160 to about 180 C., until it is again transformed into the anhydride and reconveying it into the dehydration zone for the vapors of the organic liquid. v

2. A process for dehydrating continuously ethyl alcohol which at the beginning of the process contains some water, which comprises completely dehydrating calcium sulfate at about 160 to about 180 C., vaporizingthe alcohol to be dried, distributing the anhydrous calcium sulfate, passing the alcohol vapors through the calcium sulfate in countercurrent' and in such an amount that by absorption of water the anhydrous calcium sulfate is converted into the semihydrate, withdrawing the latter from the dehydration zone, subjecting it to a temperature of about 160 to about 180 C., until it is again transformed into the anhydride and reconveying it into the dehydration zone for the alcohol vapors.

3. A process for dehydrating continuously ethyl alcohol of 95% strength which comprises completely dehydrating calcium sulfate at about 160 to about 180 C., vaporizing the alcohol to be dried, distributing the anhydrous calcium sulfate, passing the alcohol vapors through the calcium sulfate in countercurrent and in such an amount that by absorption of water the anhydrous calcium sulfate is converted into the semihydrate, withdrawing the latter from the dehydration zone, subjecting it to a temperature of about 160 to about 180 C. until it is again transformed into the anhydride and reconveying it into the dehydration zone for the alcohol vapors.

'rnnonoa warm-1s. OSKAR FALEK. 

